CN114195816A - Amino metal compound and preparation method and application thereof - Google Patents

Amino metal compound and preparation method and application thereof Download PDF

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CN114195816A
CN114195816A CN202111493995.6A CN202111493995A CN114195816A CN 114195816 A CN114195816 A CN 114195816A CN 202111493995 A CN202111493995 A CN 202111493995A CN 114195816 A CN114195816 A CN 114195816A
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nitrogen
metal compound
ammonium salt
amino
compound
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CN114195816B (en
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曹育才
杨晴
韦洪宝
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Shanghai Research Institute of Chemical Industry SRICI
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic System without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes

Abstract

The invention relates to an amino metal compound and a preparation method and application thereof, wherein the preparation method comprises the following steps: 1) taking ammonium salt containing ammonium cations as a raw material, and carrying out nitrogen anionization reaction under the action of a nitrogen anionization reagent to obtain nitrogen anionized ammonium salt; 2) the nitrogen anionized ammonium salt reacts with metal halide, and after treatment, the amino metal compound is obtained and is used for preparing the bridged metallocene compound. Compared with the prior art, the invention has convenient operation and small danger; the accurate metering is convenient, and no amine waste gas exists; small water absorption, convenient drying and direct use of the prepared product without rectification and purification.

Description

Amino metal compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation of amino metal compounds, and relates to an amino metal compound and a preparation method and application thereof.
Background
The metallocene is used as a new-generation polyolefin catalyst, can catalyze olefin monomers to polymerize to generate homo-and copolymers with highly controllable composition and structure, shows obvious advantages in the development of polymer varieties, and greatly widens the application range of polyolefin resin. The catalyst has the advantages of high polymerization activity, narrow molecular weight distribution of polymers, high comonomer uniformity, good hydrogen regulation sensitivity, rare syndiotactic polymerization characteristic and the like. Among them, the bridged metallocene catalysts are highly regarded for their excellent catalytic properties. The introduction of the bridging group increases the rigidity of the metallocene compound, and can better control the stereoselectivity of the ethyl alpha-olefin in the catalytic polymerization activity of the olefin. Many bridged metallocene compounds exist in both meso and racemic conformations, while only chiral racemic is stereotypical, and therefore stereoselective synthesis and separation of isomers of bridged metallocene compounds has become a focus of research.
Research shows that the amino metal compound has high stereoselectivity when preparing the bridged metallocene compound, and can inhibit the generation of meso compounds to a great extent to obtain racemic compounds with high purity. At present, the preparation methods of the amido metal compound mainly comprise the following two methods:
the first method comprises the following steps: adding amine into organic solvent, adding metal organic lithium compound to react to prepare amido lithium, and reacting with halogenated metal compound to prepare amido metal compound. CN103910640A reports a preparation method of tetrakis (dimethylamino) zirconium: introducing gaseous dimethylamine into an organic alkane solvent, adding a metal organic lithium compound to react to prepare an aminolithium suspension, and then reacting with zirconium tetrachloride to prepare a tetra (dimethylamino) zirconium compound. CN103193818A reports a preparation method of tetrakis (dimethylamino) titanium: introducing gaseous dimethylamine into an organic alkane solvent, adding a metal organic lithium compound to react to prepare lithium amide suspension, and then reacting with titanium tetrachloride to prepare a tetra (dimethylamino) titanium compound. US5194532A discloses the preparation of corresponding metal amides by reacting dimethylamine, diethylamine and dipropylamine, respectively, with a metal organolithium reagent followed by reaction with titanium tetrachloride. CN102417517A reports a synthesis method of tetrakis (dimethylamino) hafnium: in an n-hexane system, dimethylamine and n-butyllithium are used for preparing dimethylamino lithium, and then the dimethylamino lithium reacts with hafnium tetrachloride to prepare tetra (dimethylamino) hafnium. The method takes amine as an amine source compound, has great danger, most of gas amine is extremely easy to burn, and great damage is caused to eyes, skin and respiratory tract of a human body. In addition, the gaseous amine is not easy to meter, and may cause great feeding deviation, which in turn causes great influence on the subsequent reaction.
And the second method comprises the following steps: adding a metal organic lithium reagent into an amine aqueous solution, drying the generated amine, introducing the dried amine into an organic solvent, adding the metal organic lithium reagent to prepare an amido lithium compound, and then reacting the amido lithium compound with a halogenated metal compound to prepare the amido metal compound. CN109970786A reports a preparation method of tetrakis (dimethylamino) titanium: adding a metal organic lithium reagent into a dimethylamine aqueous solution, drying the generated dimethylamine gas, introducing the dried dimethylamine gas into an organic alkane solvent, adding the metal organic lithium reagent to prepare an amido lithium compound, and then reacting the amido lithium compound with a halogenated metal compound to prepare an amido metal compound. The method directly adds the organic lithium reagent into the amine aqueous solution, has great danger, and the metering of the amine after drying is inaccurate, thus being not beneficial to the precise control of the subsequent reaction.
In summary, the prior art directly using amine or amine aqueous solution as the raw material of the amino metal compound has the following disadvantages: (1) has certain danger and has strong stimulation to eyes, skin, respiratory tract and the like of a human body; (2) the additive has strong hygroscopicity, is not easy to measure accurately, and the residual raw materials can generate a large amount of waste gas, so that the tail gas treatment cost is greatly increased; (3) a large amount of free water is absorbed, a large amount of side reactions occur when the compound is directly used for preparing amino metal compounds, and the prepared product needs to be rectified and purified.
Disclosure of Invention
The invention aims to provide an amino metal compound and a preparation method and application thereof. The method can prepare the amido metal compound with high yield, is convenient for accurate metering and is safe to operate.
The purpose of the invention can be realized by the following technical scheme:
a method for preparing an amino metal compound, the method comprising the steps of:
1) taking ammonium salt containing ammonium cations as a raw material, and carrying out nitrogen anionization reaction under the action of a nitrogen anionization reagent to obtain nitrogen anionized ammonium salt;
2) the nitrogen anion ammonium salt reacts with the metal halide, and the amino metal compound is obtained after post treatment.
Further, the structural formula of the amido metal compound is as follows:
(R1R2NH2 +)nMm+X(m-n)，
wherein R is1、R2Independently selected from hydrogen atom, C1-C40 hydrocarbon group containing or not containing heteroatom, M is selected from transition metal of 3-12 groups, X is halogen, M is the highest oxidation state positive valence number of M, and n is the coordination number of amino.
Preferably, R1And R2Each independently selected from hydrogen atoms, heteroatom-containing or heteroatom-free hydrocarbyl groups of C1-C12, more preferably from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, cyclohexyl; x is chlorine; m is 4; m is selected from Ti, Zr, Hf, Fe, V, Nb, Ni, Cr, Mo, W, Sc, Y, lanthanides.
Further, in the step 1), the structural formula of the ammonium cation is (R)1R2NH2)+The ammonium salt is hydrochloride of ammonium cation with a structural formula of (R)1R2NH2 +)Cl-The nitrogen anionizing agent comprises one or more of methyllithium, n-butyllithium, tert-butyllithium, n-hexyllithium, sodium hydride, sodium amide, calcium hydride, potassium hydride, sodium methoxide, sodium ethoxide, sodium tert-butoxide or potassium tert-butoxide, and is preferably methyllithium, n-butyllithium, sodium hydride or potassium hydride; in the step 2), the metal halide is a halide of M.
Further, the molar ratio of the nitrogen anionizing agent to the ammonium salt is (2-4):1, preferably (2-2.5):1, and the molar ratio of the metal halide to the ammonium salt is (0.2-0.27): 1.
Further, in the step 1), the nitrogen anion reaction is carried out in an organic solvent, the feeding temperature is-78 ℃ to 10 ℃, preferably-20 ℃ to 0 ℃, the reaction temperature is room temperature, and the reaction time is 0.5-5 h. The organic solvent is preferably an ether, an alkane or an aromatic hydrocarbon solvent, and more preferably toluene or cyclohexane.
Further, in the step 2), the metal halide is mixed with the nitrogen anionized ammonium salt at-20 ℃ to 0 ℃, and then reacted at room temperature for 0.5 to 10 hours.
Further, in step 2), the post-treatment comprises filtering, washing and drying.
The above preparation steps are carried out under a dry inert atmosphere (such as nitrogen and argon), and all the organic solvents are used after being dried by molecular sieves.
Preferably, the preparation method of the amino metal compound comprises the following steps:
1) under the protection of dry atmosphere such as nitrogen, adding a hydrochloride compound of ammonium cations into a Slenk bottle provided with a thermometer and magnetic stirring, adding an organic solvent such as toluene, cyclohexane and the like, cooling to-20 ℃ to 0 ℃, slowly adding a nitrogen anionization reagent which is 2.0-2.5 molar equivalents of the ammonium salt compound, and reacting at room temperature for 0.5-5h to obtain a nitrogen anionized ammonium salt organic suspension;
2) under the protection of dry atmosphere such as nitrogen, cooling the ammonium salt suspension subjected to nitrogen anion deposition to-20 ℃ to 0 ℃, slowly adding a metal halide which is equivalent to 0.2 to 0.27 molar equivalent of the ammonium salt compound into the ammonium salt suspension, heating to room temperature, reacting for 0.5 to 10 hours to obtain an organic suspension of the amino metal compound, filtering, washing a filter cake, and drying to obtain the amino metal compound.
An amino metal compound is prepared by the method.
The use of an amino metal compound for the preparation of a bridged metallocene compound.
Further, the bridged metallocene compound has the following structural formula:
Figure BDA0003400232720000041
wherein M is1Selected from group 4 metals; x1、X2Each independently selected from halogen, substituted or unsubstituted heteroatom-containing or heteroatom-free alkyl or aryl of C1-C10; r1、R2、R3、R4、R5、R6、R7、R8Are independently selected respectivelyFrom H, C1 to C20, substituted or unsubstituted heteroatom-containing or heteroatom-free alkyl or aryl, or R1、R2、R3、R4、R5、R6、R7、R8The adjacent groups are combined through chemical bonds to form C1-C20 substituted or unsubstituted cyclopentylaryl; z is Si or an all-carbon linking group of C1-C10 with saturated valence states achieved by the substituents. The bridged metallocene compound has C2Symmetrical structure or class C2A symmetrical structure.
Preferably, Z is an ethyl or dimethylsilyl bridging chain; m1Is Ti, Zr or Hf; x1、X2Are all chlorine.
Preferably, the bridged metallocene compound is prepared using a compound of the formula:
Figure BDA0003400232720000042
under the protection of dry atmosphere such as nitrogen, adding an amino metal compound into a Slenk bottle provided with a thermometer and magnetic stirring, adding an organic solvent such as toluene and cyclohexane, and uniformly stirring to obtain an organic suspension of the amino compound; dissolving the above compound with organic solvent such as toluene and cyclohexane, adding into the organic suspension of the above amino compound at room temperature, stirring at 25-100 deg.C for 0.5-20 hr, filtering, adding trimethylchlorosilane 2.0-5.0 molar equivalent to the above compound into the filtrate, stirring for 0.2-2 hr, filtering, washing the filter cake with organic alkane reagent such as n-hexane, and drying to obtain the final product with C2Metallocene compounds of symmetrical structure.
Compared with the prior art, the method adopts ammonium salt containing ammonium cations to replace amine or amine aqueous solution as an initial raw material, performs nitrogen anionization reaction under the action of a nitrogen anionization reagent to obtain nitrogen anionized ammonium salt, and then reacts with metal halide to obtain the amino metal compound. Wherein, the ammonium salt containing ammonium cation exists in solid form, which is convenient for operation, has small hygroscopicity and is convenient for accurate metering; a small amount of water can be easily removed by utilizing the azeotropic principle of toluene and water, and the obtained product has fewer byproducts in subsequent reactions and can be directly used without further rectification and purification; in addition, because the metering is accurate in the using process, a large amount of raw material residues (even trace residues exist in a solid form) can be avoided, the generation of amine tail gas can be further avoided, and the tail gas treatment cost is reduced to a great extent.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The invention provides a preparation method of an amino metal compound, which comprises the following steps:
1) taking ammonium salt containing ammonium cations as a raw material, and carrying out nitrogen anionization reaction under the action of a nitrogen anionization reagent to obtain nitrogen anionized ammonium salt;
2) the nitrogen anion ammonium salt reacts with the metal halide, and the amino metal compound is obtained after post treatment. The structural formula of the amino metal compound is as follows:
(R1R2NH2 +)nMm+X(m-n)，
wherein R is1、R2Independently selected from hydrogen atom, C1-C40 hydrocarbon group containing or not containing heteroatom, M is selected from transition metal of 3-12 groups, X is halogen, M is the highest oxidation state positive valence number of M, and n is the coordination number of amino.
In step 1), the structural formula of the ammonium cation is (R)1R2NH2)+The ammonium salt is a hydrochloride of an ammonium cation, and the nitrogen anionizing agent comprises one or more of methyl lithium, n-butyl lithium, t-butyl lithium, n-hexyl lithium, sodium hydride, sodium amide, calcium hydride, potassium hydride, sodium methoxide, sodium ethoxide, sodium t-butoxide, or potassium t-butoxide; in the step 2), the metal halide is a halide of M. The molar ratio of the nitrogen anionizing agent to the ammonium salt is(2-4):1, and the molar ratio of the metal halide to the ammonium salt is (0.2-0.27): 1.
In the step 1), the nitrogen anion alkylation reaction is carried out in an organic solvent, the feeding temperature is-78 ℃ to 10 ℃, the reaction temperature is room temperature, and the reaction time is 0.5 to 5 hours. In the step 2), the metal halide and the nitrogen anion ammonium salt are mixed at the temperature of between 20 ℃ below zero and 0 ℃, and then the mixture is reacted for 0.5 to 10 hours at room temperature. The post-treatment comprises filtering, washing and drying.
The invention also provides an amino metal compound which is prepared by the method.
The invention also provides the application of the amino metal compound, namely the amino metal compound can be used for preparing a bridged metallocene compound. The bridged metallocene compound has the following structural formula:
Figure BDA0003400232720000061
wherein M is1Selected from group 4 metals; x1、X2Each independently selected from halogen, substituted or unsubstituted heteroatom-containing or heteroatom-free alkyl or aryl of C1-C10; r1、R2、R3、R4、R5、R6、R7、R8Each independently selected from H, C1-C20 substituted or unsubstituted heteroatom-containing or heteroatom-free alkyl or aryl, or R1、R2、R3、R4、R5、R6、R7、R8The adjacent groups are combined through chemical bonds to form C1-C20 substituted or unsubstituted cyclopentylaryl; z is Si or an all-carbon linking group of C1-C10 with saturated valence states achieved by the substituents.
Unless otherwise defined, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all commercially available conventional chemical reagents; the experimental methods are conventional methods unless otherwise specified; ammonium salts containing ammonium cations such as dimethylamine hydrochloride, methylethylamine hydrochloride, methyl n-propylamine hydrochloride, methyl isopropylamine hydrochloride and methylcyclohexylamine hydrochloride are used after being refluxed and dehydrated by dried toluene.
Example 1:
preparing an amino metal compound by using dimethylamine hydrochloride, methyllithium and zirconium tetrachloride:
weighing 8.15g of dimethylamine hydrochloride under the protection of dry nitrogen, adding the dimethylamine hydrochloride into a 250ml Slenk bottle, adding 100ml of toluene, and uniformly stirring; cooling to-15 deg.C, slowly adding 27.29g methyl lithium (3.1mol/L, diethoxymethane solution) to the reaction solution, controlling the system temperature to be less than 0 deg.C, and heating to room temperature for reaction for 2h after the addition is finished; cooling to-15 ℃, slowly adding 5.82g of zirconium tetrachloride, heating to room temperature and reacting for 8 h; the mixture was filtered, and the filter cake was washed with 20ml of n-hexane and dried to obtain 5.14g of tetrakis (dimethylamino) zirconium as a white solid with a yield of 76.93%.1HNMR(500Hz,C6D6)：σ2.96(s,24H)。
Example 2:
preparing an amino metal compound by using dimethylamine hydrochloride, n-butyl lithium and zirconium tetrachloride:
methyllithium (3.1mol/L, diethoxymethane solution) in example 1 was changed to equimolar n-butyllithium (2.5mol/L, n-hexane solution) and, without changing the conditions, 5.61g of tetrakis (dimethylamino) zirconium was obtained as a white solid with a yield of 84.00%.1HNMR(500Hz,C6D6)：σ2.96(s,24H)。
Example 3:
preparing an amino metal compound by using dimethylamine hydrochloride, n-hexyl lithium and zirconium tetrachloride:
methyl lithium (3.1mol/L, diethoxymethane solution) in example 1 was changed to equimolar n-hexyllithium (2.5mol/L, n-hexane solution), and the other conditions were not changed to obtain 4.68g of tetrakis (dimethylamino) zirconium as a white solid with a yield of 70.05%.1HNMR(500Hz,C6D6)：σ2.96(s,24H)。
Example 4:
preparing an amino metal compound by using dimethylamine hydrochloride, NaH and zirconium tetrachloride:
methyllithium (3.1mol/L, diethoxymethane solution) in example 1 was changed to equimolar sodium hydride, and the other conditions were unchanged to give tetrakis (dimethylamino) zirconium (3.47 g) as a white solid in 51.94% yield.1HNMR(500Hz,C6D6)：σ2.96(s,24H)。
Example 5:
preparing an amino metal compound by using dimethylamine hydrochloride, sodium amide and zirconium tetrachloride:
methyllithium (3.1mol/L, diethoxymethane solution) in example 1 was changed to equimolar sodium amide without changing other conditions to obtain 1.80g of tetrakis (dimethylamino) zirconium as a white solid in a yield of 27.00%.1HNMR(500Hz,C6D6)：σ2.96(s,24H)。
Example 6:
preparing an amino metal compound by using diethylamine hydrochloride, n-butyl lithium and zirconium tetrachloride:
the dimethylamine hydrochloride in example 2 was changed to equimolar diethylamine hydrochloride, and the other conditions were not changed to obtain 7.85g of colorless liquid tetrakis (diethylamino) zirconium, with a yield of 82.77%.1HNMR(500Hz,C6D6)：σ3.37(q,CH2,16H),1.16(t,CH3,24H)。
Example 7:
preparing an amino metal compound by using methyl ethylamine hydrochloride, n-butyl lithium and zirconium tetrachloride:
the dimethylamine hydrochloride in example 2 was changed to an equimolar amount of methylethylamine hydrochloride, and the other conditions were not changed to obtain 7.85g of tetrakis (methylethylamino) zirconium (iv) as a pale yellow liquid with a yield of 82.77%.1HNMR(500Hz,C6D6)：σ3.08-3.14(q,CH2,8H),2.67(t,CH3,12H),0.95-1.05(CH3,12H)。
Example 8:
preparing an amino metal compound by using methyl n-propylamine hydrochloride, n-butyllithium and zirconium tetrachloride:
the dimethylamine hydrochloride in example 2 was changed to equimolar methyl n-HClPropylamine hydrochloride, otherwise unchanged, gave 8.44g of zirconium tetrakis (methyl-n-propylamino) as a pale yellow liquid in 89.00% yield.1HNMR(500Hz,C6D6)：σ3.18-3.25(t,CH2,8H),2.92(s,CH3,12H),1.48-1.60(t,CH2,8H),0.89-0.97(t,CH3,12H)。
Example 9:
preparing an amino metal compound by utilizing methyl isopropylamine hydrochloride, n-butyl lithium and zirconium tetrachloride:
the dimethylamine hydrochloride in example 2 was changed to equimolar methyl isopropylamine hydrochloride and the other conditions were unchanged to give 8.22g of tetrakis (methyl isopropylamine) zirconium as a pale yellow liquid in 86.67% yield.1HNMR(500Hz,C6D6)：σ3.38-3.54(t,CH,4H),2.91(s,CH3,12H),1.16-1.21(t,CH3,24H)。
Example 10:
preparing an amino metal compound by using methylcyclohexyl amine hydrochloride, n-butyl lithium and zirconium tetrachloride:
the dimethylamine hydrochloride in example 2 was changed to an equimolar amount of methylcyclohexylamine hydrochloride, and the other conditions were not changed to obtain 12.81g of tetrakis (methylcyclohexylamido) zirconium as a pale yellow liquid with a yield of 95.0%.1H NMR(500Hz,C6D6)：3.05(s,CH3,12H),3.00(tt,4H),1.1-2.0(m,H4C2-C-C3H6,40H)。
Example 11:
preparing an amino metal compound by using dimethylamine hydrochloride, n-butyl lithium and hafnium tetrachloride:
by changing the zirconium tetrachloride in example 2 to an equimolar amount of hafnium tetrachloride and changing the other conditions, 7.09g of hafnium tetrakis (dimethylamino) carbonate was obtained as a white solid in an yield of 80.00%.1HNMR(500Hz,C6D6)：σ3.0(s,24H)。
Example 12:
preparing an amino metal compound by using dimethylamine hydrochloride, n-butyl lithium and titanium tetrachloride:
the zirconium tetrachloride in example 2 was changed to equimolarFurther, 4.98g of tetrakis (dimethylamino) titanium was obtained as an orange liquid in 89.00% yield under the same conditions as the other conditions.1HNMR(500Hz,C6D6)：σ3.0(s,24H)。
Example 13:
preparation of rac-ethylene bis (1-indenyl) zirconium dichloride using an amino metal compound:
under the protection of dry atmosphere such as nitrogen, 2.67g of tetra (dimethylamino) zirconium is added into a Slenk bottle provided with a thermometer and magnetic stirring, 50ml of toluene is added, and the mixture is stirred uniformly; 2.58g of 1, 2-bis-indenyl ethane was dissolved in 20ml of toluene, and added to the above-mentioned tetrakis (dimethylamino) zirconium toluene suspension at room temperature, stirred at 100 ℃ for 15 hours, filtered, 3.26g of trimethylchlorosilane was added to the filtrate, stirred for 1 hour, filtered, the filter cake was washed with 20ml of n-hexane, and dried to obtain 2.76 yellow crystals, namely rac-ethylenebis (1-indenyl) zirconium dichloride, with a yield of 65.95%.1HNMR(500Hz,CDCl3)：σ3.71-3.78(m,4H,CH2),6.21-6.22(d,2H,Cp-H),6.60(m,2H,Cp-H),7.19-7.22(m,2H,Ph-H),7.26(s,2H,Ph-H),7.32-7.34(m,2H,Ph-H),7.48-7.49(m,2H,Ph-H),7.65-7.67(m,2H,Ph-H)。
Example 14:
preparation of rac-dimethylsilylbis (1-indenyl) zirconium dichloride using an amino metal compound:
changing the 1, 2-bisindenylethane from example 13 to an equimolar 1, 2-bisindenyldimethylsilane and the other conditions were unchanged gave 2.42g of an orange solid in a yield of 54.00%.1HNMR(500Hz,CDCl3)：σ1.14(s,6H,Si-CH3),5.98-6.22(m,2H,Cp-H),6.93-6.94(m,2H,Cp-H),7.08-7.12(m,2H,Ph-H),7.36-7.39(m,2H,Ph-H),7.50-7.51(d,2H,Ph-H),7.59-7.61(d,2H,Ph-H)。
Example 15:
preparation of rac-dimethylsilylbis (2-methylindenyl) zirconium dichloride using an amino metal compound:
1.96g of an orange solid was obtained with a yield of 61.93% by changing the 1, 2-bisindenylethane in example 13 to an equimolar 1, 2-bis (2-methylindenyl) dimethylsilane and the other conditions were not changed.1HNMR(500Hz,CDCl3)：σ7.68(d,2H,indenyl),7.48(d,2H,indenyl),7.35(m,2H,indenyl),7.01(m,2H,indenyl),6.78(s,2H,indenyl H3),2.21(s,6H,2-Me),1.30(s,6H,SiMe2)。
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A method for preparing an amino metal compound, comprising the steps of:
1) taking ammonium salt containing ammonium cations as a raw material, and carrying out nitrogen anionization reaction under the action of a nitrogen anionization reagent to obtain nitrogen anionized ammonium salt;
2) the nitrogen anion ammonium salt reacts with the metal halide, and the amino metal compound is obtained after post treatment.
2. The method of claim 1, wherein the amino metal compound has the following structural formula:
(R1R2NH2 +)nMm+X(m-n)，
wherein R is1、R2Independently selected from hydrogen atom, C1-C40 hydrocarbon group containing or not containing heteroatom, M is selected from transition metal of 3-12 groups, X is halogen, M is the highest oxidation state positive valence number of M, and n is the coordination number of amino.
3. The method of claim 2, wherein the ammonium cation of step 1) is represented by the formula (R)1R2NH2)+The ammonium salt is hydrochloride of ammonium cation, and the nitrogen anionizing agent comprises one or more of methyllithium, n-butyllithium, tert-butyllithium, n-hexyllithium, sodium hydride, sodium amide, calcium hydride, potassium hydride, sodium methoxide, sodium ethoxide, sodium tert-butoxide or potassium tert-butoxide; in the step 2), the metal halide is a halide of M.
4. The method according to claim 1, wherein the molar ratio of the nitrogen anionizing agent to the ammonium salt is (2-4):1, and the molar ratio of the metal halide to the ammonium salt is (0.2-0.27): 1.
5. The method of claim 1, wherein the step 1) comprises the step of anionizing the nitrogen in an organic solvent at a temperature of-78 ℃ to 10 ℃, at room temperature, and for a period of 0.5 to 5 hours.
6. The method of claim 1, wherein the metal halide is mixed with the ammonium salt of nitrogen anion at-20 to 0 ℃ in the step 2), and then reacted at room temperature for 0.5 to 10 hours.
7. The method according to claim 1, wherein the post-treatment in step 2) comprises filtering, washing and drying.
8. An amino metal compound, characterized in that it is prepared by the process according to any one of claims 1 to 7.
9. Use of an amino metal compound according to claim 8 for the preparation of a bridged metallocene compound.
10. The use of an amino metal compound according to claim 9, wherein the bridged metallocene compound has the following formula:
Figure FDA0003400232710000021
wherein M is1Selected from group 4 metals; x1、X2Each independently selected from halogen, substituted or unsubstituted heteroatom-containing or heteroatom-free alkyl or aryl of C1-C10; r1、R2、R3、R4、R5、R6、R7、R8Each independently selected from H, C1-C20 substituted or unsubstituted heteroatom-containing or heteroatom-free alkyl or aryl, or R1、R2、R3、R4、R5、R6、R7、R8The adjacent groups are combined through chemical bonds to form C1-C20 substituted or unsubstituted cyclopentylaryl; z is Si or an all-carbon linking group of C1-C10 with saturated valence states achieved by the substituents.
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US5194532A (en) * 1990-09-20 1993-03-16 The Dow Chemical Company Homogeneous catalysts and olefin polymerization process
CN103910640A (en) * 2014-03-18 2014-07-09 南京大学 Synthetic method of tetra(dimethylamino)zirconium
CN107188908A (en) * 2017-06-26 2017-09-22 江苏南大光电材料股份有限公司 Three（Dimethylamino）The preparation method of cyclopentadienyl group zirconium
CN112745366A (en) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 Silicon-based bridged metallocene compound and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5194532A (en) * 1990-09-20 1993-03-16 The Dow Chemical Company Homogeneous catalysts and olefin polymerization process
CN103910640A (en) * 2014-03-18 2014-07-09 南京大学 Synthetic method of tetra(dimethylamino)zirconium
CN107188908A (en) * 2017-06-26 2017-09-22 江苏南大光电材料股份有限公司 Three（Dimethylamino）The preparation method of cyclopentadienyl group zirconium
CN112745366A (en) * 2019-10-30 2021-05-04 中国石油化工股份有限公司 Silicon-based bridged metallocene compound and preparation method and application thereof

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